Melting Point of cis-1,4-Polybutadiene

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Abstract
Melting point values for cis-1, 4-polybutadiene thus far reported in the literature have not exceeded +1° C. Varying values have been reported, both because of sample variations (differing amounts and distributions of chain imperfections) and because of variations in experimental techniques used to measure the melting point (in particular, varying heating rates). Some workers have extrapolated their data to predict that the melting point of a perfectly regular (100 per cent cis) cis-1, 4- polybutadiene (Tm°) would be close to +1° C. These extrapolations have been used to arrive at heats of fusion for the polymer from Flory's theory for melting point depression due to copolymeric impurities. One such value has been used in another investigation to estimate extents of crystallization from thermodynamic data. We wish to report observation of melting points several degrees higher than the assumed Tm° value of +1° C. Our experiments show that these higher values are not due to orientation effects.

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